The intermolecular rotational potential energies for poly(dimethylsiloxane) (PDMS) chains are directly obtained from a priori probability P-alpha beta. Here the differing statistical weight matrices for the Si-O and O...The intermolecular rotational potential energies for poly(dimethylsiloxane) (PDMS) chains are directly obtained from a priori probability P-alpha beta. Here the differing statistical weight matrices for the Si-O and O-Si bonds are considered in calculating the configuration partition function. In the Bahar's model, as the same statistical weight matrices for the Si-O and O-Si bonds are adopted, there exists a large deviation of a priori probability P-alpha beta between the theory and the molecular dynamics (MD) simulation. Our model gives satisfactory agreement with experiment on the mean-square unperturbed end-to-end distance, the mean-square dipole moment and its temperature dependence, and the molar cyclization equilibrium constants for dimethylsiloxane oligomers. This new rotational isomeric state approach can be widely applied to other chains; such as -CH2-C[(CH2)(m)H](2)- and -O-Si[(CH2)(m)H](2) for arbitrary m.展开更多
Chiroptical properties including electronic circular dichroism（ECD） and optical rotatory dispersion（ORD） of artemisinin and artemether have been fully studied using quantum-chemical calculation based on time-depen...Chiroptical properties including electronic circular dichroism（ECD） and optical rotatory dispersion（ORD） of artemisinin and artemether have been fully studied using quantum-chemical calculation based on time-dependent density functional theory.Both theoretical ECD and ORD of these two compounds were in good match with the experimental data.ECD spectrum of artemether could be totally attributed to the peroxide group,and that of artemisinin was an overlay of contribution from δ-lactone and peroxide moieties,which leading to a positive maximum at 260 nm.Our results showed that peroxide group could produce a broad ECD band in the far-UV region originated from electron transitions of HOMO →LUMO,HOMO-1 →LUMO and HOMO-2 →LUMO in the case of artemether.This work provided a theoretical interpretation of the ECD behavior of peroxide bond.展开更多
基金This research was financially supported by National Natural Science Foundation of China and the National Basic Research Project"Macromolecular Condensed State"from STCC.
文摘The intermolecular rotational potential energies for poly(dimethylsiloxane) (PDMS) chains are directly obtained from a priori probability P-alpha beta. Here the differing statistical weight matrices for the Si-O and O-Si bonds are considered in calculating the configuration partition function. In the Bahar's model, as the same statistical weight matrices for the Si-O and O-Si bonds are adopted, there exists a large deviation of a priori probability P-alpha beta between the theory and the molecular dynamics (MD) simulation. Our model gives satisfactory agreement with experiment on the mean-square unperturbed end-to-end distance, the mean-square dipole moment and its temperature dependence, and the molar cyclization equilibrium constants for dimethylsiloxane oligomers. This new rotational isomeric state approach can be widely applied to other chains; such as -CH2-C[(CH2)(m)H](2)- and -O-Si[(CH2)(m)H](2) for arbitrary m.
基金supported by the Fundamental Research Funds for the Central Institutes of China(No.2012ZD03)
文摘Chiroptical properties including electronic circular dichroism（ECD） and optical rotatory dispersion（ORD） of artemisinin and artemether have been fully studied using quantum-chemical calculation based on time-dependent density functional theory.Both theoretical ECD and ORD of these two compounds were in good match with the experimental data.ECD spectrum of artemether could be totally attributed to the peroxide group,and that of artemisinin was an overlay of contribution from δ-lactone and peroxide moieties,which leading to a positive maximum at 260 nm.Our results showed that peroxide group could produce a broad ECD band in the far-UV region originated from electron transitions of HOMO →LUMO,HOMO-1 →LUMO and HOMO-2 →LUMO in the case of artemether.This work provided a theoretical interpretation of the ECD behavior of peroxide bond.
